Production of coloring-matters of the anthraquinone series.



i iooo wow or manunsm, GERMANY, assrenon T namscns ANILIN & sons YABRIK, U LUDWIGSEAFEN-01l'-THE-REINE, GERMANY, A CORPORATION OF BADEN.

record-non or concerns-marinas or one eiz 'rrraaeolnonn snares.

$133598 Ho Drawing.

To. all whom it concern Be it known that l, Hoco "il otrr, citizen of the German Empire, residing at'Mannheirs Germany, have invented neiv and useful "improvements in the lroduction of Coloring-Matters of the Anthraquinone Series, of which the following is a specification.

I have found that by treating a l-arylainino-anthraquinone containing a methyl group in the ortho position to the nitrogen atom 'with a halogenizin ence of a suitable solvenl, such for instance as nitrobenzene or trichlorbenzene, anthraquinone-acridones can be obtained which, according to the method of carrying out the reaction, will contain more or less halogen. The methyl 'group in the ortho position to the nitrogen atom can be either in the aryl residue or in the anthraquinonyl residue. As instances of halogenating agents I mention chlorin, broinin and sulturyl chlorid, without however restricting myself to these specific agents. The products yield intensely colored rats and dye regetal'ilc fiber brilliant shades of excellent fastness.

The following examples \i'ill serve to illustrate further the nature of this invention, which, however, is not confined to these eX- an les. The parts are by Weight.

vexample 1: lass'a currentof chlorin into a solution containing parts of l-anilino- Z-niethyl-anthraqninone and a small quantity of iodin in 100 parts of nitrobenzene, While maintaining the temperature at about 160 C. When a test portion shows that no initial material remains unaltered, filter off the crystalline product, Wash it with benzone, and dry it. The coloring ma'ttenwhich contains chl'orin, is obtained in the form 0 YlOlGb-bl'OWll leaflets which yield a red-yellow solution in concentrated sulfuric acid,

while rater precipitates the coloring matter in the form of violet-red flakes. /Vith alkaine hydrosuli'ite a blue-violet vat is obtained hich dyes cotton red with a violet tinge.

.The coloring matter yicldsa red solution in tiltrobenzene and other organic solvents of 11gb boiling point. A similar or identical l roduct can also be obtained by treating 1-ortho-toluido-anthraquinone in a similar manner.

Example 2: Pass gaseous chlorin for several hours into 200 parts of trichlor-benzene Specification of letters Eatent.

Application filed September 26, 1913.

.ture of from 150 agent in the preslow-brown solution benzene and 120 parts of bromin,

Patented Mar, 23, 1915.

Serial No. 791,951.

containing parts anthraquinone. If desired a reagent that will bind hydrochloric acid, such as calcined soda, and traces of water may be addedto the reaction mixture. Maintain a temperato 170 oil the product, wash it dry it, A chloranthraquinone-acridone is obtained in the form of brown-red leaflets; It yields an orange-red mass is cold, filter with benzene and solution in concentrated sulfuric acid and is .65

om this solution by means of Water, giving clue-red flakes. With alkaline hydrosulfite a vielet-brown vat is obtained which dyes cotton very tast red shades with a blue tinge. The coloring blue-red, solution in nitrobenzene. The product obtained asabove described is new and apparently consisting of a miyture of tetrachlorand pent'aohior-anthrnquinone precipitated t acridones. it, in this example, the l-anilino- 75 Q-methybanthraquinone be replaced by 1- para c lo'r aniline-2-methyl-anthraquinonc (obtainable, for instance, from para-chloranilin and l-nitr0-2 methyl anthraquinonel,

a coloring matter 18 obtained which posso sesses similar properties.

On subjecting 1- naphthylamino-Z-inethyl antliraquinone to treatment with chlorin'in the inanner described above, a naohthanthraquinonefacridone is obtained in the form of a brown- 85 red crystalline powder which yields a yelin concentrated sulfuric acid! It dissolves in nitrobenzene giving a blue-red solution and yields a violet-brown vatwith alkaline hydrosulfite, vat cotton is dyed red-brown.

Example 3: Boil together gently, in a reflux apparatus, parts of 1-anilino-2-- methyl-antbraquinone, 500 parts of nitroportion shows that no unaltered initial material remains. Allow the mass to cool, then filter off the crystals and wash them with benzene. The brozn-anthraquinoneacridone consists of a' violetbrown crystal 100 line powder which yields a blue-red solution in nitrobenz'ene and a red-brown solution in concentrated sulfuric acid. On pouring the sulfuric acid solution of l-anilino-Q-miethyl- C. When the matter yields a from which so until a test into Water, v10letbrown flakes areobtained which yield a violet ya from 'Wl'llCh cotton is a few hours, into parts benzene as the solvent, and further the reaction can, if desired, be carried out at a lower temperature, v v Example 4: Pass chloriii, for

of l orth otolnido-anthraquinone contained in 150 parts of trichlor-benzene, while maintainiiag t e temperature at from 160 to 170 Then the mass is cool, filter off the browna current of red crystalline coloring matter which can be purifieclby extraction with boiling glacial or identical the foregoing Example 2. 4

'with I ture' of; from 160 tained in the form 0 Heat together for several. hours, in a reflux apparatus, at from 170 to 175 (1, 1-0 parts of 'l-ortho-toluidm anthraquinone, parts of nitrobenzene and 25 parts of bromin. en the mass is cool, filter off the coloring matter which is similar to, or identical with the brom-i Xample 5 'anthraquinone-acridone obtainable accordin alto thefore oin'g Exampleii.

llxample 6: issolve 20 parts of l-orthotoluido-,6-cl 1lor-anthraquinone' (obtainable by boiling 1'-ii'itro -6-chlor-anthra'uinone ortho-toluidin) in parts 0 nitrobenzene and, while .maintaining a temperato 0., pass a current solution until a test porof chlorin into the l unaltered initial material tlon shows that no 4 is present. he mass to cool and then filter of! the coloring matter which is obsmall violet-red crysta s. It dissolves in concentrated sulfuricwashing and drying, becomes reddish violet.

violetshades which,upon

Similar coloring matters can from the, isomeric 1-ortho-toluido-5-chloranthraQi-i'ihone and l-ortliostoluidoJ-chlor anthraquinone. v 1 Now what I claim i'swv he process of producing coloring matters of the anthraqmnone series b'y'treating, with a halogenizmg agent the presence of a suitable solvent, a I-aryl-am'inogroup anthraquinone with chlorin at a raisedi'tem perature and in th e presence of trichlorhenzene, which new col 1n the form of brown-red leaflets, which be obtained.-

oring matter is a chlor 'anthraqumoneacridone and can be obtained yields anoran ge-red solution in concentra w A h e-red solution in nitro nzene, and with alkaline hydrosulfite gives a violet brown vat which dyes cotton very fast red shades with a blue tinge;

In testimony whereof I have hereunto set my hand in the presence'of two'subscribin r w1tnesses. i

, HUGO woLFF,

LLOYD, Joan-n Pmmrm;

Water," "givingibluered flakes,- which' coloringematter yields a 

